滇重楼药材中无机元素与有效成分的相关性研究

Research on the Correlation of Inorganic Elements and Active Ingredients in Paris polyphylla

目的：研究滇重楼药材中无机元素与有效成分的相关性。方法：采用高效液相色谱法（HPLC）测定药材中重楼皂苷Ⅰ、Ⅱ、Ⅵ、Ⅶ的含量：色谱柱为Phenomenex C18,流动相为乙腈-水（梯度洗脱）,流速为1.0 ml/min,检测波长为203 nm,柱温为30℃。采用电感耦合等离子体质谱法（ICP-MS）测定药材中钠（Na）、镁（Mg）、钾（K）、钙（Ca）、铬（Cr）、锰（Mn）、铁（Fe）、镍（Ni）、锌（Zn）、硒（Se）、锶（Sr）、钼（Mo）、铅（Pb）、镉（Cd）、汞（Hg）、铜（Cu）、砷（As）的含量：射频功率为1.55 k W,采样深度为10 mm,等离子气体流量为15.0 ml/min,载气流速为0.86 L/min,雾化室温度为2℃,碰撞模式为He,载气流量为4.5 ml/min,测量点数/峰为6,数据采样模式为跳峰采集（重复采集3次）。所得数据采用SPSS 21.0软件进行逐步回归分析,以评价上述两者的相关性。结果：重楼皂苷Ⅰ、Ⅱ、Ⅵ、Ⅶ检测进样量线性范围分别为0.939～4.697μg（r=0.999 9）、1.124～5.620μg（r=0.999 6）、0.784～3.918μg（r=0.999 8）、0.976～4.880μg（r=0.999 9）;精密度、稳定性、重复性试验的RSD〈2%;加样回收率分别为96.53%～100.71%（RSD=1.69%,n=6）、98.19%～99.55%（RSD=0.58%,n=6）、95.45%～100.83%（RSD=1.87%,n=6）、96.11%～102.01%（RSD=2.07%,n=6）。17种无机元素检测含量线性范围为0～195.984 3 mg/kg（r≥0.999 3）;检测限≤65.201 ng/kg。重楼皂苷Ⅰ含量与Mg呈正相关,与Pb呈负相关;重楼皂苷Ⅱ含量与Cu呈正相关,与As呈负相关;重楼皂苷Ⅵ含量与Sr、Hg呈正相关,与Mn呈负相关;重楼皂苷Ⅶ含量与Na、Ni呈正相关,与As呈负相关;4种重楼皂苷总含量与Ni、Sr呈正相关,与Fe呈负相关。结论：滇重楼药材中无机元素含量与有效成分存在一定相关性。

OBJECTIVE：To study the correlation of inorganic elements and active ingredients in Paris polyphylla. METHODS：HPLC was adopted for contents determination of polyphyllinⅠ,Ⅱ,Ⅵ and Ⅶ：the column was Phenomenex C18 with mobile phase of acetonitrile-water（gradient elution）at a flow rate of 1.0 ml/min,detection wavelength was 203 nm,and column temperature was 30 ℃. ICP-MS was adopted for contents determination of Na,Mg,K,Ca,Cr,Mn,Fe,Ni,Zn,Se,Sr,Mo,Pb,Cd,Hg,Cu and As：RF power was 1.55 k W,sampling depth was 10 mm,the plasma gas flow was 15.0 ml/min,carrier gas flow rate was 0.86 L/min,spray chamber temperature was 2 ℃,helium collision mode was He,gas flow was 4.5 ml/min,measurement points/peak was 6,sampling mode was hopping peak collection（repeated 3 times）. And SPSS 21.0 software was adopted for stepwise regression analysis of correlation between the two above-mentioned. RESULTS：The linear range was 0.939-4.697 μg（r=0.999 8）for polyphyllinⅠ,1.124-5.620 μg（r=0.999 6）polyphyllinⅡ,0.784-3.918 μg for polyphyllin Ⅵ,0.976-4.880 μg for polyphyllin Ⅶ.RSDs of precision,stability and reproducibility tests were lower than 2%,recoveries were 96.53%-100.71%（RSD=1.69%,n=6）for polyphyllinⅠ,98.19%-99.55%（RSD=0.58%,n=6）forⅡ,95.45%-100.83%（RSD=1.87%,n=6）for polyphyllin Ⅵ,96.11%-102.01%（RSD=2.07%,n=6）for polyphyllin Ⅶ. The linear range was 0-195.984 3 mg/kg（r≥0.999 3）,detection limit was no higher than 65.201 ng/kg. PolyphyllinⅠshowed positive correlation with Mg and negative correlation with Pb;polyphyllin Ⅱ showed positive correlation with Cu and negative correlation with As;polyphyllin Ⅵ showed positive correlation with Sr and Hg and negative correlation with Mn;polyphyllin Ⅶ showed positive correlation with Na and Ni and negative correlation with As;the total contents of the 4 polyphyllins showed positive correlation with Ni and Sr and negative correlation with Fe. CONCLUSIONS：The contents of inorganic elements and P. polyphylla have certain correlation with active ingredient.